The ferroelectric crystal Ba2TiSi2O8 with high second-order optical nonlinearity is precipitated in Sm3+-doped BaO-TiO2-SiO2 glass by a focused 800 nm,250 kHz and 150 fs femtosecond laser irradiation.No apparent blue and red emissions are observed at the beginning,while strong blue emission due to second harmonic generation and red emission due to the f-f transitions of Sm3+ are observed near the focal point of the laser beam after irradiation for 25 s. Micro-Raman spectra confirm that Ba2TiSi2O8 crystalline dots and lines are formed after laser irradiation.The mechanism of the phenomenon is discussed.